[0001] This invention concerns a method for making methanol in a liquid-phase methanol reactor
wherein a metanol-forming catalyst is entrained in an inert liquid and contacted with
a synthesis gas comprising hydrogen and carbon monoxide.
[0002] In United States Patent No. 3,888,896 to Espino et al., issued June 10, 1975, methanol
is prepared from carbon monoxide and hydrogen by saturating an inert organic liquid
medium, such as pseudocumene, with the carbon monoxide and hydrogen and contacting
the saturated liquid medium with a methanol forming catalyst. Both fixed bed and fluidized
bed catalysis are described. For fixed bed operation, suitable catalyst particle sizes
are said to range from about 3200 to about 6400 microns whereas particle sizes of
from about 200 to about 4800 microns are recommended for fluidized beds.
[0003] United States Patent No. 4,031,123 to Espino et al., issued June 21, 1977, discloses
a process for forming methanol by contacting carbon monoxide, carbon dioxide and hydrogen
with a bed of methanol-forming catalyst contained in a paraffinic or cycloparaffinic
liquid so as to limit the concentration of the methanol in the liquid during the reaction.
It is said that the catalyst bed may be fixed or slurried in, or fluidized by, the
liquid. Depending upon the bed type utilized, i.e., fixed, fluidized or slurried,
and the liquid flow rate employed, suitable average particle sizes are said to range
from about 190 to about 6400 microns. For fluidized bed operation, the preferred particle
size is said to be between 16 and 20 mesh, i.e., from about 850 to about 1000 microns.
[0004] Sherwin and Frank, in Make Methanol by Three Phase Reaction, Hydrocarbon Processing
(November 1976), pages 122-124, describe a methanol synthesis process using an inert
circulating hydrocarbon to fluidize a heterogeneous catalyst bed which controls the
heat of the exothermic reaction. Catalyst activity is said to increase with decreasing
particle size over the region of 1000 to 3000 microns but not in direct proportion.
[0005] Kolbel et al., in Proc. European Syms. Chem. React. Eng., 3rd, Pergamon Press, Oxford
(1965) at 115, report of a study regarding the hydrogenation of carbon monoxide to
methane in a reactor where Ni - MgO catalyst was suspended in a parafifinic hydrocarbon.
The Institute Francais due Petrole process for the hydrogenation of benzene to cyclohexane
with a Raney nickel catalyst uses the cyclohexane product as a circulating liquid
to carry the catalyst out the bottom of the reactor, through external heat exchangers
and back into the top of the reactor. See Dufau et al., CEP, 60 (1964) at 43 and Cha
et al., Oil and Gas Journal (June 10, 1974). Similar reaction systems are noted in
Ostergaard, Advances in Chemical Engineering, Vol. 7, Academic Press, New York at
71. Most commonly, it is assumed that in systems wherein the catalyst is entrained
in a liquid the catalyst remains captive within the reactor and that mixing is accomplished
either by stirring or by rising gas bubbles. See Ostergaard, supra; Govindarao, Chemical
Engineering Journal, 9 (1975) at 229; and Roy et al., Chemical Engineering Science,
19 (1964) at 216.
[0006] Heretofore the preferred method of liquid-phase methanol production included use
of a fluidized bed catalyst, wherein a circulating inert liquid hydrocarbon and the
synthesis gas feed were cocurrently introduced into the bottom of a reactor and the
hydrocarbon liquid, with some assistance from the gas feed, fluidized the catalyst.
In such a system, the physical limits of the reaction zone, co-extensive with the
volume of the fluidized catalyst bed, are controlled principally by such factors as
catalyst particle size and the velocity of the liquid hydrocarbon. The previously
preferred method is not without its undesirable aspects. For example, total control
of the fluidized bed requires relative uniformity of catalyst particle size, otherwise
liquid velocities sufficient to fluidize large particles will carry small particles
out of the desired reaction zone. Even when catalyst particles of a uniform suitable
size are initially charged to the reactor, attrition of the particles, a virtually
unavoidable consequence of the constant motion of particles in a fluidized bed and
the inherent difficulties of producing a catalyst particle that will not be attrited
in such an environment, eventually results in an undesirable distribution of particle
size and the formation of catalyst fines. Entrainment of catalyst fines in the gas
or liquid exiting the reactor leads to the diminution of catalyst in the fluidized
bed and also creats problems in downstream process equipment. Also, the velocity of
the inert liquid hydrocarbon circulating through the reactor is limited by the necessity
of retaining the fluidized catalyst particles within the desired boundaries of the
reaction zone. Thus the hydrocarbon liquid, which functions as a heat sink for the
highly exothermic synthesis reaction, usually possesses a significant temperature
gradient over the length of its passage through the reactor. Control of reaction temperature
is therefore significantly hindered. A still further consequence of the relatively
low liquid velocities required by the fluidized bed process lies in the necessity
of cooling the hydrocarbon liquid externally of the reactor, since the poor heat transfer
characteristics attributable to the low velocity preclude cooling the liquid inside
the reactor, for example by means of a cooling coil.
[0007] One object of this invention is to provide a liquid phase methanol synthesis process
in which the attrition of catalyst particles is virtually eliminated as a problem.
A further object is to provide such a process wherein a great range of fluid velocities
through the reactor may be utilized. A still further object of the invention is to
provide a liquid phase methanol reaction process permitting significantly greater
control over temperature profiles within the reactor.
[0008] The process of the present invention utilizes relatively small catalyst particles
entrained in an inert hydrocarbon liquid as opposed to a fluidized catalyst bed in
the liquid phase production of methanol. Among the advantages of the present process
are savings in catalyst costs, the availability of higher temperature operation of
the reactor and improved temperature profiles within the reactor, and the use of less
expensive reactors.
[0009] Catalyst costs are reduced through the combined effect of several aspects of the
new entrained catalyst process as compared to the fluidized bed method. The preparation
of catalyst particles for the fluidized bed liquid phase methanol production system
typically requires obtaining catalyst powder and, through use of suitable binders,
pelletizing the catalyst into particles of uniform size that will resist attrition.
In the present process, the catalyst may be used in the powdered form and, therefore,
significant preparatory work may be avoided. As presently understood, the controlling
mechanism in the liquid-phase methanol synthesis is the mass transfer of reactant
across the liquid film surrounding the catalyst particles, whether the system under
consideration incorporates a fluidized bed or the entrained catalyst process. Diminishing
the catalyst particle size results in increasing the available surface area of catalyst,
thereby decreasing the resistance to mass transfer. Thus smaller catalyst particle
size leads to increased catalyst productivity per unit weight, requiring that less
catalyst be charged to the reactor to reach a given production level. Also, the catalyst
particles of smaller size are less susceptible to attrition, resulting in the formation
of less catalyst fines and the alleviation of problems downstream of the reactor attributable
thereto. Finally, the rate of catalyst replacement in the reactor is reduced with
the elimination of the need to maintain catalyst pellets of a uniform size in the
reactor. Attrition of pellets becomes an irrelevant consideration rather than a cause
for catalyst replacement.
[0010] Higher temperature reactor conditions with the entrained catalyst system are feasible
because of the higher reactivities attainable without adverse effect on methanol yields.
Increased reactor operating temperatures allow recovery of the exothermic heat of
reaction as higher pressure steam.
[0011] Improved temperature profiles within the reactor represent another potential benefit
of the entrained catalyst process. For example, use of a countercurrent reactor configuration,
which is simply not an option with the fluidized bed system, results in temperature
profiles that improve CO conversion by allowing product gases to exit the reactor
at the cold end of the liquid feed, thereby gaining a 20-30°C advantage in the thermodynamically-limited
CO conversion. Also, the higher fluid velocities possible with the instant process
result in improved gas-liquid heat transfer characteristics and consequently improved
temperature profiles within the reactor. Higher fluid velocities also result in enchanced
reaction rates since they improve gas-liquid mass transfer characteristics.
[0012] The foregoing advantages of the entrained catalyst process combine to allow the construction
of less expensive, greater length-to-diameter ratio reactors for given levels of production.
[0013] In the process of the present invention, the catalyst in powdered form, preferably
having a particle size of less than 125 microns, and more preferably from 10 to 125
microns, is purposefully suspended in an inert hydrocarbon liquid and the catalyst
entrained in a liquid is circulated through the reactor. Thus rather than being required
to judiciously determine and set appropriate fluid velocities through the reactor
and/or suitable catalyst pellet size in order to fix the desired boundaries of a fluidized
catalyst bed, one using the liquid-entrained catalyst system of the present invention
may set fluid velocities through the reactor solely on the basis of other considerations.
[0014] The ability to increase the velocity of the inert hydrocarbon liquid and entrained
catalyst through the reactor provides several options not available to the practitioner
of the heretofore preferred fluidized bed liquid phase methanol process. Rather than
encountering a significant gradient from the inlet to outlet liquid temperatures,
for example, the liquid may be circulated through the reactor at a rate great enough
so that the temperature gradient of the liquid can be markedly reduced. Thus a relatively
narrow optimum reactor temperature range highly favorable to equilibrium conditions
may be maintained and the highly exothermic reaction may proceed under conditions
approaching isothermal.
[0015] Since higher liquid velocities through the reactor significantly increase the potential
for good heat transfer between the liquid and heat exchange means within the reactor
itself, the liquid-entrained catalyst system permits avoidance of heat-exchange external
of the reactor and allows removal of excess heat via a cooling coil in the reactor,
for example. Also, since the catalyst, which preferably makes up to 5 to 40 weight
percent of the liquid-catalyst mixture, provides additional heat capacity as compared
to the fluidized bed system, the volumetric circulation rate of process liquid will
be lower with the entrained catalyst system.
[0016] The liquid hydrocarbon employed must be capable of dissolving at least small amounts
of hydrogen, carbon monoxide, and methanol; must be stable and substantially inert;
and most of it must remain liquid in the reactor at the temperature and pressure employed.
Naturally, the catalyst must not dissolve or react with the liquid. Generally, the
vapor pressure of the liquid should not exceed 34x 1 05 Pa (34 atm. abs. or 500 psia)
at a temperature of 250°C. Organic compounds are preferred.
[0017] Examples of compounds which may be used are aromatics, such as alkylated naphthalenes
having 10 to 14 carbon atoms, alkylated biphenyls having 12 to 14 carbon atoms, and
polyalkylbenzenes having 7 to 12 carbon atoms and 1 to 5 alkyl substitution groups
(e.g., pseudocumene, xylene, and diethylbenzene); saturated alcohols having from 5
to 20 carbon atoms (e.g., cyclohexanol and n-octyl alcohol); saturated esters having
from 5 to 15 carbon atoms (e.g., n-amyl acetate and ethyl n-valerate); saturated paraffins
(including cycloparaffins) having 6 to 30 carbon atoms (e.g., hexane, dimethylpentane,
and hexadecane); and blends of the foregoing, with paraffins and aromatics being preferred.
[0018] The reaction temperature is broadly from 100 to 500°C, preferably from 200 to 400°C,
and most desirably from 215 to 275°C. Pressures of 1.38x10
g to 6.89×10
7 Pa (200 to 10,000 psia), preferably from 3.44x106 to 2.41 x 10
7 Pa (500 to 3,500 psia), and most desirably from 3.44x 1 06 to 1.03 x 107 Pa (500
to 1,500 psia), may be employed. The ratio of hydrogen to carbon monoxide in the feed
gas is preferably from 0.6 mole of hydrogen per mole of carbon monoxide up to 10 moles
per mole. Other gases, such as carbon dioxide and methane, may be present in the synthesis
gas. The flow rate of reactants is broadly from 0.1 to 10 kgs of feed gas per kg of
catalyst per hour and preferably from 0.3 to 5.
[0019] The liquid flow through the reactor should be sufficient to prevent excessive temperature
rise, and is generally from 200 to 20,000 grams per gram-mole of methanol produced
and preferably from 500 to 10,000.
[0020] The catalyst employed can be any methanol-forming catalyst active within the specified
temperature range, i.e., 100 to 500°C. Methanol-forming catalysts are described in
detail in the following literature references: French Patent No. 1,489,682; Shokubai
(Tokyo) 1966, 8, 279-83; U.S.S.R. Patents Nos. 219.569; 264,355; 269,924; and 271,497;
German Patent No. 1,300,917; Khim. Prom. Ukr. 1969 (6), 7-10; Kogyo Kagaku Zassi 1969,
72 (11), 2360-3; German Patent Publications Nos. 2,016,596; 1,930,702; 2,026,182;
2,026,165; 2,056,612; 2,165,379; and 2,154,074; Khim Ind. (Sofia) 1971, 43 (10), 440-3.
The active elements of the methanol-forming catalysts which may be used include copper,
zinc, aluminum, magnesium, zinc chromium, molybdenum, uranium, tungsten, vanadium
and rare earths. The low- temperature methanol catalysts, such as those described
in U.S. Patent No. 3,326,956, are especially useful. The amount of catalyst entrained
in the inert liquid can vary as desired or required with from 5 to 40 weight percent
catalyst in the inert liquid being preferred.
[0021] One version of a three-phase liquid-entrained catalyst reactor system is shown in
Figure 1. Synthesis gas feed comprising hydrogen and carbon monoxide is preheated
by reactor product gas in heat exchanger 1, combined with recycle gas and fed to the
bottom of reactor 2 through a series of standard orifices to distribute gas bubbles
throughout the reactor. The liquid-catalyst mixture, preferably comprising approximately
5-40 weight percent methanol catalyst powder in paraffinic oil and coming from surge
drum 12 by way of circulating oil pump 13 and heat exchanger 4, enters the top of
reactor 2 just below the vapor disengagement zone 3. The liquid-catalyst mixture enters
at a temperature of approximately 240°C and, as it travels downward in the reactor,
increases in temperature by absorbing the heat liberated in the methanol reaction.
The synthesis and product gases, flowing countercurrently, are gradually cooled as
they rise to the top of the reactor. The countercurrent flow of gases and liquid-catalyst
has a beneficial thermodynamic effect in that the gases exiting the reactor are cooler
than when the fluidized bed catalyst is used and the lower temperature favors the
methanol reaction equilibrium. Because of the lower temperature, the circulating oil
vapor pressure will be lower than in the fluidized bed system. This decreases the
load on the condensed oil return system and therefore increases the overall thermal
efficiency of the process.
[0022] The liquid and entrained catalyst exit the bottom of reactor 2 and enter an agitated
surge drum 12, which prevents liquid-catalyst separation. High pressure steam can
be generated from boiler feed water at heat exchanger 4 before recycle of the liquid
and catalyst through the reactor. Circulation through the heat exchanger unit must
be carefully controlled to prevent any buildup of solids, fouling and erosion.
[0023] The reactor product gas is cooled by first preheating synthesis gas feed at heat
exchanger 1, then recycle gas at heat exchanger 5, then boiler feed water at heat
exchanger 6 and is given a final cooling by air or cooling water at heat exchanger
7. Methanol and any vaporized process liquid are condensed and separated in the vapor-liquid
separator 8. The methanol stream produced is suitable for fuel use directly or can
be sent to a distillation system (not shown) to produce chemical grade product. Unconverted
gases are recycled back to the reactor via recycle compressor 9 and heat exchanger
5.
[0024] In order to reduce or eliminate the carryover of catalyst fines from the reactor
by the product gas stream, the reactor may be designed to include a disengagement
zone at the top. For example, the velocity of the product gas stream at the top of
the reactor could be reduced by providing an expansion zone. The larger cross- sectional
area of such a zone would result in a lower flow velocity of the exiting gas within
the zone and reduce the likelihood of catalyst fines being carried from the liquid
by the product gas and exiting the reactor along with the product gas. Where the reactor
is cylindrical in form and vertically oriented, the disengagement zone could include
an expansion zone in the form of an inverted truncated cone, with the small diameter
end of such a zone being of the same diameter as the reactor and located just above
the upper level of liquid in the reactor and with the product gas exiting the reactor
at the large diameter end of the zone.
[0025] Tests were performed with commercial calcined methanol catalyst to compare reaction
rates to be reasonably expected as between use of an entrained catalyst system and
use of a system relying on a fluidized bed. These different catalyst forms were approximated
by use of catalyst of a particle size equivalent to that which would be used under
the relevant condition. In all cases the catalyst was reduced by standard procedures
in the dry state, slurried into mineral oil at 15 weight percent and then charged
to an agitated stainless steel reactor. The reactor was heated to 225-230°C and a
synthesis gas feed comprising 50% H
Z, 25% C0, 10% C0
2 and 15% CH
4 by volume was sparged into the stirred reactor at 35x 1 05 Pa (35 atmospheres).
[0026] The preceding tests were run for three catalyst particle size distributions: (1)
37-74 micron cut (200x400 mesh) screened from catalyst powder; (2) 149-177 micron
cut (80x 100 mesh) screened from crushed catalyst tablets; and (3) 2380 micron catalyst
(3/32x3/32-inch tablets). The data of Table I were taken without aging the catalysts
and the results are illustrated in Figure 2, where CO conversion is plotted against
weight hourly space velocity (WHSV).
[0027] As evidence by Figure 2, the highly preferred entrained catalyst particle size of
37-74 microns yields, at commercially practical flow rates, significantly greater
CO conversion than obtained with the larger particles. Indeed, at low flow rates reactions
using the catalyst particles sized from 37 to 74 microns virtually reach the calculated
equilibrium conversion point.
[0028] Figure 3 is a cross-plot of the CO conversion-WHSV relationships shown in Figure
2. In Figure 3, however, the conversion parameter shows the relative rate of CO conversion
in the entrained catalyst mode to that of the fluidized bed mode. At low space velocity
there is little discrepancy between the two reaction modes but at higher space velocities,
which are commercially feasible, the entrained mode yields a CO conversion equivalent
to 4 or 5 times that of the fluidized mode and therefore requires only 20-25% of the
catalyst necessary for equivalent production via a fluidized bed operation.
1. A process for making methanol wherein the process is conducted in a liquid-phase
methanol reactor by contacting a synthesis gas comprising hydrogen and carbon monoxide
with a methanol-forming catalyst in the presence of an inert liquid, characterised
in that said catalyst is entrained in said inert liquid, said catalyst is in the form
of particles of a size less than 125 microns, and said inert liquid is an inert hydrocarbon
liquid which is capable of dissolving at least small amounts of hydrogen, carbon monoxide
and methanol and which is such that most of the inert liquid remains in the reactor
at the temperature and pressure involved.
2. A process according to claim 1 characterised in that the catalyst particle size
is greater than 10 microns.
3. A process according to claim 1 or claim 2 characterised in that the reactor temperature
is from 100°C to 500°C.
4. A process according to any of the preceding claims characterised in that the reactor
pressure is from 1.38x 106 to 6.89 x 1 07 Pa (200 psia to 10,000 psia).
5. A process according to any of the preceding claims characterised in that the inert
liquid comprises at least one of the alkylated naphthalenes having 10 to 14 carbon
atoms; alkylated biphenyls having 12 to 14 carbon atoms; polyalkylbenzenes having
7 to 12 carbon atoms and 1 to 5 alkyl substitution groups; saturated alcohols having
5 to 20 carbon atoms; saturated esters having 5 to 15 carbon atoms; and saturated
paraffins having 6 to 30 carbon atoms.
6. A process according to any of the preceding claims characterised in that the reactor
temperature is from 215°C to 275°C and the reactor pressure is from 3.44x 106 to 2.41 x 107 Pa (500 to 1,500 psia).
7. A process according to any of the preceding claims characterised in that the amount
of catalyst entrained in the inert liquid is from 5 to 40 weight percent.
8. A process for preparing methanol wherein the process is conducted in a liquid-phase
methanol reactor by contacting a synthesis gas comprising hydrogen and carbon monoxide
with a methanol-forming catalyst in the presence of an inert liquid, characterised
in that the process includes the steps:
(a) entraining from 5 to 40 weight percent of methan-forming catalyst particles in
an inert hydrocarbon liquid, said particles having a size from 10 to 125 microns;
(b) contacting said synthesis gas with said entrained catalyst reactor at a temperature
of from 215°C to 275°C and a pressure of from 3.44×106 to 2.41 X107 Pa (500 to 1,500 psia); and
(c) separating methanol from the catalyst, inert liquid and unreacted synthesis gas,
the inert liquid being a liquid which is capable of dissolving at least small amounts
of hydrogen, carbon monoxide and methanol and which is such that most of the inert
liquid remains in the reactor at the temperature and pressure involved.
9. A process according to any of the preceding claims characterised in that said synthesis
gas and said catalyst entrained in said liquid are countercurrently introduced into
said reactor.
10. A process according to any of the preceding claims characterised in that said
synthesis gas also comprises carbon dioxide and methane.
11. A process according to any of the preceding claims characterised in that product
gas exiting said reactor is passed through a disengagement zone located between the
upper level of liquid in the reactor and reactor exit for said product gas.
12. A process according to any of the preceding claims characterised in that said
reactor comprises internal cooling means.
13. A process for making methanol wherein the process is conducted in a liquid-phase
methanol reactor by contacting a synthesis gas comprising hydrogen and carbon monoxide
with a methanol forming catalyst in the presence of an inert liquid, characterised
in that the catalyst is entrained in said inert liquid, said catalyst being in the
form of particles of a size of from 37 to 74 microns, the reactor temperature being
from 215°C to 275°C and the reactor pressure being from 3.44x 106 to 2.41 x 107 Pa (500 to 1,500 psia), and said inert liquid is an inert hydrocarbon liquid which
is capable of dissolving at least small amounts of hydrogen, carbon monoxide and methanol
and which is such that most of the inert liquid remains in the reactor at the temperature
and pressure involved.
1. Verfahren zur Methanolherstellung, das in einem Flüssigphasen-Methanolherstellungs-Reaktionsbehälter
durch Inberührungbringen bzw. Kontaktbehandlung eines Wasserstoff und Kohlenmonoxid
enthaltenden Synthesegases mit einem Methanolbildungskatalysator in Gegenwart einer
inerten Flüssigkeit durchgeführt wird, dadurch gekennzeichnet, daß der Katalysator
in der inerten Flüssigkeit mitgeführt wird, der Katalysator in Form von Teilchen mit
einer Größe von weniger als 125 um vorliegt und die inerte Flüssigkeit eine inerte
Kohlenwasserstoff-Flüssigkeit ist, die imstande ist. mindestens kleine Mengen von
wasserstoff, Kohlenmonoxid und Methanol aufzulösen, und so beschaffen ist, daß der
größte Teil der inerten Flüssigkeit bei der Temperatur und dem Druck, die in Frage
kommen bzw. angewandt werden, in dem Reaktionsbehälter verbleibt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Teill-chengröße des
Katalysators mehr als 10 um beträgt.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Reaktionsbehältertemperatur
100°C bis 500°C beträgt.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
der Reaktionsbehälterdruck 1,38 bis 68,9 MPa (200 psia bis 10.000 psia) beträgt.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
die inerte Flüssigkeit mindestens einen Vertreter von alkylierten Naphthalinen mit
10 bis 14 Kohlenstoffatomen, alkylierten Biphenylen mit 12 bis 14 Kohlenstoffatomen,
Polyalkylbenzolen mit 7 bis 12 Kohlenstoffatomen und 1 bis 5 Alkylsubstitutionsgruppen,
gesättigten Alkoholen mit 5 bis 20 Kohlenstoffatomen, gesättigten Estern mit 5 bis
15 Kohlenstoffatomen und gesättigten Paraffinen mit 6 bis 30 Kohlenstoffatomen enthält.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
die Reaktionsbehältertemperatur 215°C bis 275°C beträgt und der Reaktionsbehälterdruck
3,44 bis 24,1 MPa (500 bis 1.500 psia) beträgt.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
die Menge des in der inerten Flüssigkeit mitgeführten Katalysators 5 bis 40 Gew.-%
beträgt.
8. Verfahren zur Methanolherstellung, das in einem Flüssigphasen-Methanolherstellungs-Reaktionsbehälter
durch Inberührungbringen bzw. Kontaktbehandlung eines Wasserstoff und Kohlenmonoxid
enthaltenden Synthesegases mit einem Methanolbildungskatalysator in Gegenwart einer
inerten Flüssigkeit durchfefühurt wird, dadurch gekennzeichnet, daß das Verfahren
die folgenden Schritte enthält:
(a) Mitführung von 5 bis 40 Gew.-% Teilchen des Methanolbildungskatalysators in einer
inerten Kohlenwasserstoff-Flüssigkeit, wobei die Teilchen eine Größe von 10 bis 125
,um haben,
(b) Inberührungbringen des Synthesegases mit dem mitgeführten Katalysator bei einer
Reaktionsbehältertemperatur von 215°C bis 275°C und einem Reaktionsbehälterdruck von
3,44 bis 24,1 MPa (500 bis 1.500 psia) und
(c) Abtrennung von Methanol von dem Katalysator, inerter Flüssigkeit und nicht umgesetztem
Synthesegas, wobei die inerte Flüssigkeit eine Flüssigkeit ist, die imstande ist,
mindestens kleine Mengen von Wasserstoff, Kohlenmonoxid und Methanol aufzulösen, und
so beschaffen ist, daß der größte Teil der inerten Flüssigkeit bei der Temperatur
und dem Druck, die in Frage kommen bzw. angewandt werden, in dem reaktionsbehälter
verbleibt.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
das Synthesegas und der in der Flüssigkeit mitgeführte Katalysator im Gegenstrom in
dem Reaktionsbehälter eingeführt werden.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
das Synthesegas auch Kohlendioxid und Methan enthält.
11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
das aus dem Reaktionsbehälter ausströmende Produktgas durch eine Ausscheidungs- bzw.
Trennzone hindurchgeleitet wird, die sich zwischen dem oberen Spiegel der Flüssigkeit
in dem Reaktionsbehälter und dem Reaktionsbehälterauslaß für das Produktgas befindet.
12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß
der Reaktionsbehälter eine Einrichtung für die Innenkühlung aufweist.
13. Verfahren zur Methanolherstellung, das in einem Flüssigphasen-Methanolherstellungs-Reaktionsbehälter
durch Inberührungbringen bzw. Kontakbehandlung eines Wasserstoff und Kohlenmonoxid
enthaltenden Synthesegases mit einem Methanolbildungskatalysator in Gegenwart einer
inerten Flüssigkeit durchgeführt wird, dadurch gekennzeichnet, daß der Katalysator
in der inerten Flüssigkeit mitgeführt wird, wobei der Katalysator in Form von Teilchen
mit einer Größe von 37 bis 74 pm vorliegt, die Reaktionsbehältertemperatur 215°C bis
275°C beträgt und der Reaktionsbehälterdruck 3,44 bis 24,1 MPa (500 bis 1.500 psia)
beträgt, und daß die inerte Flüssigkeit eine inerte Kohlenwasserstoff-Flüssigkeit
ist, die imstande ist, mindestens kleine Mengen von Wasserstoff, Kohlenmonoxid und
Methanol aufzulösen, und so beschaffen ist, daß der größte Teil der inerten Flüssigkeit
bei der Temperatur und dem Druck, die in Frage Kommen bzw. angewandt werden, in dem
Reaktionsbehälter verbleibt.
1. Procédé de production de méthanol où le procédé est entrepris dans un réacteur
de méthanol en phase liquide par mise en contact d'un gaz de synthèse comprenant de
l'hydrogène et de l'oxyde de carbone avec un catalyseur formant du méthanol en présence
d'un liquide inerte, caractérisé en ce que ledit catalyseur est entraîné dans ledit
liquide inerte, ledit catalyseur a la forme de particules d'une dimension inférieure
à 125 microns, et ledit liquide inerte est un hydrocarbure liquide inerte capable
de dissoudre au moins de faibles quantités d'hydrogène, d'oxyde de carbone et de méthanol
et qui est tel que la plus grande partie du liquide inerte reste dans le réacteur
à la température et à la pression mises en cause.
2. Procédé selon la revendication 1, caractérisé en ce que la dimension des particules
du catalyseur est supérieure à 10 microns.
3. Procédé selon la revendication 1 ou la revendication 2 caractérisé en ce que la
température du réacteur est de 100°C à 500°C.
4. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que la pression du réacteur est de 1,38x 106 à 6,89x 107 Pa (200 psia à 10 000 psia).
5. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que le liquide inerte comprend au moins l'une parmi des naphthalènes alcoylées ayant
de 10 à 14 atomes de carbone' des biphényles alcoylés ayant de 12 à 14 atomes de carbone;
des poly- alkylbenzènes ayant de 7 à 12 atomes de carbone et 1 à 5 groupes de substitution
d'alcoyles; des alcools saturés ayant de 5 à 20 atomes de carbone; des esters saturés
ayant de 5 à 15 atomes de carbone; et des paraffines saturées ayant de 6 à 30 atomes
de carbone.
6. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que la température du réacteur est de 215 à 275°C et la pression du réacteur est de
3,44x 106 à 2,41 x 107 Pa (500 à 1 500 psia).
7. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que la quantité du catalyseur entraîné dans le liquide inerte est de 5 à 40% en poids.
8. Procédé de préparation de méthanol où le procédé est entrepris dans un réacteur
de méthanol en phase liquide par mise en contact d'un gaz de synthèse comprenant de
l'hydrogène et de l'oxyde de carbone avec un catalyseur formant du méthanol en présence
d'un liquide inerte, caractérisé en ce que le procédé comprend les étapes de:
(a) entraîner de 5 à 40% en poids des particules du catalyseur formant du méthanol
dans un hydrocarbure liquide inerte, lesdites particules ayant une dimension de 10
à 125 microns;
(b) mettre en contact ledit gaz de synthèse avec ledit catalyseur réacteur entraîné
à une température de 215°C à 275°C et une pression de 3,44×106 à 2,41 x 107 Pa (500 à 1 500 psia); et
(c) séparer le méthanol du catalyseur, du liquide inerte et du gaz de synthèse n'ayant
pas réagi, le liquide inerte étant un liquide capable de dissoudre au moins des petites
quantités d'hydrogène, de l'oxyde de carbone et du méthanol et qui est tel que la
plupart du liquide inerte reste dans le réacteur à la température et à la pression
mises en cause.
9. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que ledit gaz de synthèse et ledit catalyseur entraîné dans ledit liquide sont introduits
à contre-courant dans ledit réacteur.
10. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que le gaz de synthèse contient également du gaz carbonique et du méthane.
11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en
ce que le gaz produit sortant dudit réacteur passe à travers une zone de dégagement
quie est placée entre le niveau supérieur du liquide dans le réacteur et la sortie
du réacteur pour ledit gaz produit.
12. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce
que ledit réacteur comprend un moyen de refroidissement interne.
13. Procédé de production de méthanol où le procédé est entrepris dans un réacteur
de méthanol en phase liquide par mise en contact d'un gaz de synthèse comprenant de
l'hydrogène et de l'oxyde de carbone avec und catalyseur formant du méthanol en présence
d'un liquide inerte, caractérisé en ce que le catalyseur est entraîne dans ledit liquide
inerte, ledit catalyseur ayant la forme de particules d'une dimension de 37 à 74 microns,
la température dans le réacteur étant de 215 à 275°C et la pression dans le réacteur
étant de 3,44x 106 à 2,41 X 1 07 Pa (500 à 1 500 psia) et le ledit liquide inerte est un hydrocarbure
liquide inerte capable de dissoudre au moins des petites quantités d'hydrogène, d'oxyde
de carbone et de méthanol et qui est tel que la plus grande partie du liquide inerte
reste dans le réacteur à la température et à la pression mises en cause.